This invention relates to a semi-tension mask (also called semi-stretched-tension mask or SST mask) formed of a Fexe2x80x94Ni alloy for use in a cathode-ray tube or picture tube (formerly Braun tube) and, more particularly, to a Fexe2x80x94Ni alloy which has excellent magnetic properties and is outstandingly capable of controlling beam drift under the influence of geomagnetism of a mask made of it, a semi-tension mask made of the alloy, and a color picture tube using the semi-tension mask.
A picture tube is provided with a perforated mask as a mechanism through which electron beams from electron guns precisely strike the intended color phosphor dot on a phosphor screen to give a desired color tone. Masks for picture tubes are roughly divided into two types; shadow mask type or a mask workpiece formed with dots or slots for the passage of electron beams by etching and then formed to the mask shape by pressing, and aperture grille type or a mask workpiece formed with elongated slits for the passage of electron beams by etching and then pulled vertically and tentered or stretched on a frame.
For the shadow mask type, Fe-36% Ni alloy (invar) is commonly used as it controls the doming phenomenon that results from thermal expansion. For the aperture grille type whose structural features rarely allow doming due to thermal expansion, mild steel that is higher in the coefficient of thermal expansion but is less expensive is employed.
With both advantages and disadvantages the two types have dominated the market. More recently, what is known as semi-tension mask has come on the scene as a new type combining the merits of the former two.
The semi-tension mask is made by vertically stretching a mask workpiece that has been formed with dots or slots for the passage of electron beams by etching and supporting it on a frame (tentering) rather than pressing the sheet, as in the aperture grille type. In the early stage of its development, the mask needed its workpiece be stretched not only vertically but also horizontally, i.e., in a total of four directions. The four-direction stretching sometimes broke the mask workpieces. To preclude this danger, experiments were made on stretching the workpieces only in two vertical directions and favorable results were obtained. The mask made by the improved method of stretching the workpiece with weak forces in two directions, rather than in four directions, is designated semi-stretched tension mask, or briefly semi-tension mask.
FIGS. 1 and 2 are schematic views illustrating, respectively, a semi-tension type mask and an aperture grille type mask. Both masks are stretched vertically, or upwardly and downwardly. In a semi-tension mask a multiplicity of columns of vertical slots are formed from edge to edge. Each column of slots comprises a number of slots separated by bridges formed between the ends of adjacent slots. An aperture grille mask, by contrast, has a multiplicity of long vertical slits extending from nearly top to nearly bottom and arranged sidewise from edge to edge. It requires damper wires to control the vibration of the mask that is caused by sound sources such as speakers. The bridges of a semi-tension mask are the portions left unetched when the slots have been formed by etching. They serve to prevent the columns of vertical slots from being twisted. Because of the presence of bridges in the individual columns of slots, the mask is also called a bridged tension mask.
Compared with the shadow mask type formed by press work, the semi-tension mask type permits the picture tube to be more flattened with greater brightness and higher resolution. Moreover, the presence of bridges enables the semi-tension type to be superior to the aperture grille type in vibration resistance, with no necessity of damper wire. Further, the former requires relatively low loads for vertical stretching, which helps reduce the cost.
On the other hand, the semi-tension mask type has the possibility of doming with thermal expansion due to the low stretching force and bridging, as compared with the aperture grille type. To prevent the phenomenon, the use of Fexe2x80x94Ni alloys of low thermal expansion, especially invar, is under study. It has, however, been found that the use of invar that has hitherto been used for superfine color display in the manufacture of a semi-tension mask causes a problem of serious beam drift along edges of the mask. Ordinarily a semi-tension mask is made substantially flat for flat picture tubes (center height of the curved screen/diagonal length of the screen  less than 0.1%). Thus at the edges of the mask the angle that a beam makes with the mask is small at the edges, with the consequence that a slight beam drift of an electron beam from an electron gun results in an increased amount of mislanding on the phosphor. One of the intended features of a semi-tension mask is to obtain high luminance by increasing the aperture ratio. This sacrifices the magnetic shield characteristic of the mask itself to such an extent that beam drift is likely to take place.
Another problem is wrinkling of the mask. In the manufacture of a semi-tension mask a workpiece formed with dots or slots by etching is blackened, welded to a frame, and stretched under predetermined loads. Here the term xe2x80x9cblackenxe2x80x9d is used to mean a treatment in which a mask workpiece is heated in a steam or combustion gas atmosphere to form a black film such as an iron oxide film on the surface so that the mask looks black. The blackened work is stretched under given loads, welded to a frame, and baked to be freed of strains that have resulted from welding and other operation. It has recently been found that, during the baking, the invar sheet under tension by the frame undergoes plastic deformation at elevated temperature, or creeping. Once it occurs, creeping causes elongation of the mask and the xe2x80x9ctension downxe2x80x9d or relief of loads which, in turn, lead to wrinkling, deterioration of vibration characteristics, and various other problems. Thus the drawbacks of the semi-tension mask type include the tension down upon baking in the course of the fabrication, leading to wrinkling and other major troubles.
From the viewpoint of thermal expansion, mild steel and the like are not suited as materials for semi-tension mask, and it has been necessary to use a low-thermal-expansion alloy such as invar, with improved magnetic shield characteristic. When used in the manufacture of a semi-tension mask, the invar that is used for a shadow mask of the pressed type with no magnetic shield problem, deteriorates the magnetic shield characteristic of the semi-tension mask. Careful investigation of the manufacturing steps has revealed that this difference is caused by a significant change in the magnetic characteristic of the material with stretching, i.e., before and after the stretching.
To be more concrete, it is necessary with the pressed type shadow mask to allow its bridges (the portions between the apertures in the form of dots or slots through which electron beams pass) to have sufficient (self-shape-retaining) strength to keep its shape (curvature). In order to attain high luminance, the etching factor (amount of etching in the depth direction/amount of side etching) should be high so as to form a multiplicity of dots or slots by etching while securing the bridges, and for that purpose it is customary to treat the workpiece in such a manner as to avoid the collection in the rolled surface of the closest packed (111) plane where the corrosion rate is low. We tentered the material on a frame, stretching it in the rolling direction (the  less than 100 greater than direction) and in the directions ( less than 110 greater than  directions) at angles of 90xc2x0 and 45xc2x0 to the rolling direction, and these magnetic properties were determined. With a geomagnetic shield after AC demagnetization as in a picture tube, the higher the residual magnetic flux density (Br) and the smaller the coercive force (Hc), the better the magnetic shield properties. Hence the magnetic shield properties are improved as the relative magnetic permeability calculated as Br/Hc, xcexcBr/Hc, increases. It has been found that a sheet tentered both in the rolling direction and in the transverse direction to the rolling direction showed less relative magnetic permeability xcexcBr/Hc than when not tentered and exhibited inferior magnetic shield properties, whereas a sheet stretched in the direction at an angle of 45xc2x0 to the rolling direction gave greater relative magnetic permeability xcexcBr/Hc and better magnetic shield properties. It has also been found that the relative magnetic permeability xcexcBr/Hc varies with the blackening temperature and the stresses applied for stretching. However, working a mask blank from a strip obliquely at an angle of 45xc2x0 is not practicable because of much material loss it involves.
The present invention is aimed at introducing measures whereby favorable magnetic shield properties of a semi-tension mask are secured and color irregularity or mislanding due to beam drift can be prevented. Another aim of the invention is to improve the creep properties of a semi-tension mask in view of the fact that when ordinary invar is used for a semi-tension mask, baking in the course of mask fabrication causes tension-down of the material, leading to wrinkling and other serious problems.
It has now been found possible to secure magnetic shield properties and preclude color irregularity or mislanding on the phosphor due to beam drift by controlling the sum of the X-ray intensity ratio of (111) plane and (220) plane in the rolled surface of a Fexe2x80x94Ni alloy. It has also been found that the sum of the X-ray intensity ratio of (111) plane and (220) plane can be controlled according to the blackening temperature of the semi-tension mask and the stresses of stretching the mask. It has further been found that the creep properties of a Fexe2x80x94Ni alloy can be improved without wrinkling and other troubles in the course of blackening, stretching, and baking for the manufacture of a semi-tension mask by choosing proper proportions of Al and Si and restricting the proportions of impurities C, P, and S in the alloy, and performing stress relief annealing of the alloy.
On the basis of the above discoveries, the present invention solves the problems of the prior art by providing:
(1) A Fexe2x80x94Ni alloy for semi-tension mask comprising from 34 to 45% Ni, from 0.01 to 0.5% Mn, and the balance Fe and unavoidable impurities, said alloy being such that a sheet obtained after final cold rolling has xcex1(111)+(220), said sum of the X-ray intensity ratio of (111) plane and (220) plane in the rolled surface represented by Formula 1                              α                                    (              111              )                        +                          (              220              )                                      =                                                            I                                  (                  111                  )                                            +                              I                                  (                  220                  )                                                                                    I                                  (                  111                  )                                            +                              I                                  (                  200                  )                                            +                              I                                  (                  220                  )                                            +                              I                                  (                  311                  )                                                              xc3x97          100          ⁢                      xe2x80x83                    ⁢                      (            %            )                                              (        1        )            
of no less than 15%;
(2) A Fexe2x80x94Ni alloy according to (1) wherein, assuming that the temperature for blackening the mask is Txc2x0 C. and the stress for stretching it as a semi-tension mask is xc3x3N/mm2, the xcex1(111)+(220) in the sheet surface after the final cold rolling satisfies Formula 2
xe2x88x920.28Txe2x88x920.1"sgr"+218xe2x89xa6xcex1(111)+(220)xe2x89xa655(%);xe2x80x83xe2x80x83(2)
(3) A low thermal-expansion Fexe2x80x94Ni alloy according to (1) or (2) which further comprises from 0.005 to 0.20% Si and from 0.005 to 0.030% Al;
(4) A Fexe2x80x94Ni alloy according to (1), (2), or (3) wherein, out of the unavoidable impurities, C accounts for no more than 0.010%, P for no more than 0.015%, and S for no more than 0.010%;
(5) A Fexe2x80x94Ni alloy according to any of (1) to (4) which is subjected to stress relief annealing after the final cold rolling.
The present invention also provides:
(6) A semi-tension mask made from the Fexe2x80x94Ni alloy according to any of (1) to (5) by the steps of forming dots or slots for the passage of electron beams by etching in a mask workpiece of the Fexe2x80x94Ni alloy, blackening, stretching the blackened workpiece in two directions or upwardly and downwardly, and then stretching the same on a frame; and
(7) A color picture tube using the semi-tension mask according to (6).
As explained above, FIG. 1 schematically illustrates a semi-tension type mask. The mask is tentered on a frame as stretched vertically, or upwardly and downwardly. In the semi-tension mask a multiplicity of columns of vertical slots are formed over the entire width. Each slot column has a number of slots separated from one another by a bridge defined between the ends of adjacent slots. The bridges in a semi-tension mask constitute unetched portions between slots in the columns left after the slots have been formed by etching. They serve to prevent twisting of the columns of vertical slots. Compared with the shadow mask formed by pressing, the semi-tension mask can be more precisely flattened with higher brightness and higher resolution. In addition, the semi-tension mask is superior in vibration characteristics to the aperture grille type. It requires no damper wire and less loads for stretching it in two vertical directions, both of which contribute to the reduction of the manufacturing cost.
The semi-tension mask according to the present invention uses a Fexe2x80x94Ni alloy comprising from 34 to 45% Ni, from 0.01 to 0.5% Mn, desirably from 0.005 to 0.20% Si and from 0.005 to 0.030% Al, and the balance Fe and unavoidable impurities, in which preferably C is limited to no more than 0.010%, P to no more than 0.015%, and S to no more than 0.010%.
The semi-tension mask of the invention is manufactured in the following way. A Fexe2x80x94Ni alloy of a predetermined composition is melted in a vacuum melting furnace, and the ingot so obtained is forged and hot rolled to a thickness from 2 to 4 mm. It is then repeatedly cold rolled and bright annealed to form a cold rolled sheet from about 0.3 mm to about 0.11 mm thick. Following recrystallization annealing, it is finally cold rolled to a thickness of 0.1 mmxc2x10.05 mm as a mask material. Preferably, the final cold rolling is followed by a stress relief annealing at 350 to 500xc2x0 C. for from 10 minutes to one hour. The mask sheet is then degreased and coated with a photoresist on both sides, exposed to light for patterning. After developing, the surface is sprayed with an etching solution consisting essentially of aqueous ferric chloride to form dots or slots by etching. The etched sheet is blackened in a steam or combustion gas atmosphere at 580 to 670xc2x0 C., stretched both upwardly and downwardly, and welded in a tentered state to a frame, whereby a semi-tension mask is made. Lastly, the mask is baked at 350 to 500xc2x0 C. for from 10 minutes to one hour to remove strains that have resulted from welding and other operations.
The greatest feature that characterizes the present invention is that magnetic shield properties are secured and color irregularity or mislanding on the phosphor due to beam drift is suppressed by controlling the sum of the X-ray intensity ratio of (111) plane and (220) plane in the rolled surface of a Fexe2x80x94Ni alloy.
We made mask blanks from an invar strip of Fexe2x80x94Ni alloy for pressed masks having a (111) plane X-ray intensity ratio of less than 1%, by etching the blanks so that the longitudinal direction of their grids were at intervals of 5xc2x0 in the range from 0 to 45xc2x0 to the rolling direction, blackening the masks at 640xc2x0 C., and stretching them under a load of 100 N/mm2, and then examined the amounts of drift of the beam that passed the grids. In the meantime, test specimens were cut off in rectangles at angles from 0 to 45xc2x0 to the rolling direction. They were stretched at 100 N/mm2, their hysteresis loops at the maximum magnetic field of 3183 A/m, and their relative magnetic permeability xcexcBr/Hc values were computed. It was then confirmed that the beam drift can be suppressed to a satisfactory level if the relative magnetic permeability xcexcBr/Hc is 2400 or more.
It was also confirmed that magnetic shield properties can be secured by changing the sum of the X-ray intensity ratio of (111) plane and (220) plane in the rolled surface as well as by changing the angle of sampling from a strip having a (111) plane X-ray intensity ratio of less than 1%.
In brief, we have found that magnetic shield properties can be secured and color irregularity or mislanding on the phosphor due to beam drift be precluded by controlling the sum of the X-ray intensity ratio of (111) plane and (220) plane in the rolled surface of a Fexe2x80x94Ni alloy. The sum of the X-ray intensity ratio of (111) plane and (220) plane can be controlled according to the blackening temperature of the semi-tension mask and the stresses of stretching the mask.
In the manufacture of a semi-tension mask a workpiece formed with dots or slots by etching is blackened, welded to a frame, and stretched under predetermined loads. The blackened work is baked to be freed of strains that have resulted from welding and other operation. During the baking, the invar sheet under tension by the frame undergoes plastic deformation at elevated temperature, or creeping. Once it occurs, creeping causes elongation of the mask and the xe2x80x9ctension downxe2x80x9d or relief of loads which, in turn, lead to wrinkling, deterioration of vibration characteristics, and various other problems. The present invention improves the mask in respect of the creeping.
The grounds on which various limitations are placed under the invention will now be explained.
Ni:xe2x80x94A Ni content less than or more than 36% increases the coefficient of thermal expansion and deteriorates the color purity of the resulting mask. If the Ni content is below 34% the thermal expansion coefficient rises rapidly, the softening temperature declines, the proof stress after blackening decreases, and the creep elongation upon tentering tends to increase. For these reasons the lower limit of Ni is 34%.
If the Ni content is more than 36%, the thermal expansion coefficient of the alloy increases but the softening temperature rises too, limiting the drop of proof stress after blackening, and increasing the stretching forces to prevent the deterioration of its doming tendency due to thermal expansion. Moreover, the larger the Ni content the better the magnetic properties of the alloy. However, if the Ni content exceeds 45%, the alloy is little different from mild steel in respect of thermal expansion and economically there is no merit of employing the Fexe2x80x94Ni alloy for a semi-tension mask. Hence the Ni content is specified to be between 34 and 45%.
Mn:xe2x80x94Mn is needed because it makes S, an impurity that hampers hot workability, harmless. In a proportion below 0.01% it no longer achieves the favorable effect and, above 0.5%, it deteriorates the etching properties and raises the coefficient of thermal expansion. For these reasons the Mn proportion is limited to the range between 0.01 and 0.5%. A preferred range for the improvements of etching and thermal expansion properties is between 0.01 and 0.1%.
Si:xe2x80x94Si is added as a deoxidant. Since a large Si content seriously affects etchability, a small content is desirable. Even in a small amount, Si is effective in improving creep properties, and therefore the range is between 0.005 and 0.20%. For better etching properties a range from 0.03% downward is preferred.
Al:xe2x80x94Al is utilized as a deoxidant, and a solid solution containing much Al proves effective in improving creep properties. However, a large Al content forms alumina to impair the etchability or produces alumina-derived surface flaws on cold rolling. The range, therefore, is between 0.005 and 0.030%.
C:xe2x80x94C form a carbide, but more than 0.010% C forms the carbide to excess, impairing etchability. For this reason 0.010% is the upper limit. C in a solid solution too affects the etchability adversely, and the smaller the C content the better. A preferred C proportion is below 0.005%.
P:xe2x80x94Excessive P causes inferior etching. The P content should be kept below 0.015%.
S:xe2x80x94S in excess of 0.010% has a detrimental effect upon hot workability, while forming much sulfide inclusions which, in turn, impairs etchability. Hence the upper limit of 0.010%.
xcex1(111)+(220), said sum of the X-ray intensity ratio of (111) plane and (220) plane in the rolled surface: The xcex1(111)+(220) materially influences the magnetic properties of the mask material when stretched in the directions parallel to the rolling direction and transverse to the rolling direction. When the xcex1(111)+(220), is small, the relative magnetic permeability of the mask material upon stretching is low and the magnetic shield properties are unfavorably affected. To secure proper magnetic shield properties, the xcex1(111)+(220) should be at least 15%.
Here the xcex1(111)+(220) is a value calculated by Formula 1, which is defined as:                               α                                    (              111              )                        +                          (              220              )                                      =                                                            I                                  (                  111                  )                                            +                              I                                  (                  220                  )                                                                                    I                                  (                  111                  )                                            +                              I                                  (                  200                  )                                            +                              I                                  (                  220                  )                                            +                              I                                  (                  311                  )                                                              xc3x97          100          ⁢                      xe2x80x83                    ⁢                      (            %            )                                              (        1        )            
In order to increase the xcex1(111)+(220) it is necessary to restrict the reduction ratio of cold rolling. Since it involves an increase in the frequency of annealing, extra cost is required. Also, the xcex1(111)+(220) being the same, the relative magnetic permeability would be increased if the temperature for blackening the mask were high. The xcex1(111)+(220), therefore, desirably falls within the range of Formula 2 that is obtained experimentally from the relation between the blackening temperature Txc2x0 C. and the stress of stretching xc3x3N/mm2:
xe2x88x920.28Txe2x88x920.1"sgr"+218xe2x89xa6xcex1(111)+(220)xe2x89xa655(%)xe2x80x83xe2x80x83(2)
Formulas 1 and 2 will now be explained.
A Fexe2x80x94Ni alloy consisting of 36.1% Ni, 0.25% Mn, and the balance iron and unavoidable impurities was refined by vacuum melting and the ingot was hot forged and hot rolled to a sheet 3 mm thick and then was descaled by pickling. Next, to vary the xcex1(111)+(220), said sum of the X-ray intensity ratio of (111) plane and (220) plane, test sheets were annealed once or twice and cold rolled at several different reduction ratios to a thickness of 0.13 mm. These materials were annealed for recrystallization and then cold rolled to a thickness of 0.1 mm. The crystal orientations of their rolled surfaces were determined by X-ray diffraction analysis and the xcex1(111)+(220) values were found. The test materials were blackened at different temperatures of 580, 600, and 640xc2x0 C. for 15 minutes, and were subjected to tensile stresses of 100, 150, and 200 N/mm2 in the direction parallel to the rolling direction. From hysteresis loops in the maximum magnetic field of 3183 A/m, their relative magnetic permeability xcexcBr/Hc values were determined.
FIGS. 3 to 5 show the relations between the xcex1(111)+(220) of the rolled surface after final cold rolling and the relative magnetic permeability xcexcBr/Hc, with different tensile stresses and blackening temperatures. Of the combinations of the tensile stresses and blackening temperatures, the xcex1(111)+(220) values of the rolled surfaces after final cold rolling at the relative magnetic permeability xcexcBr/Hc of 2400 that was judged to cause no beam drifting were found, as given in Table 1. It will be obvious from the table that the xcex1(111)+(220) at a blackening temperature below 640xc2x0 C. (above which and closer to the softening temperature the strength decreases) and a stretching stress below 200 N/mm2 (above which and closer to the proof stress the creep elongation increases) is desirably above 15%. On the basis of the results given in Table 1, the left-hand side member of Formula 2 was obtained by finding an approximate expression of the xcex1(111)+(220) at which the relative magnetic permeability xcexcBr/Hc was 2400 or more, using the two variables blackening temperature T C and tensile stress xc3x3N/mm2.
Table 1. The xcex1(111)+(220) values of the finally cold rolled surfaces where the relative magnetic permeability xcexcBr/Hc was 2400 at varied blackening temperatures and tensile stresses
If the xcex1(111)+(220) value of a finally cold rolled surface is to be small, the reduction ratio of the cold rolling before the final annealing should be low. When the reduction ratio is low the subsequent recrystallization annealing brings a duplex grain structure. The upper limit of the xcex1(111)+(220) value of the finally cold rolled surface made at the limit of reduction ratio just short of a duplex grain structure was 55%. This gave the right-hand side member of Formula 2, and eventually Formula 2 was determined.
Lastly, the final cold rolling reduction ratio and stress relief annealing will be explained.
Final cold rolling reduction ratio:xe2x80x94When the ratio of reduction by final cold rolling is less than 15%, improvement of strength by the work hardening is small and the creep-improving effect is not quite appreciable. On the other hand, when the reduction ratio is more than 60%, the material begins to soften during blackening treatment which, in turn, affects the high-temperature strength and creep properties unfavorably. Hence the final cold rolling reduction ratio desirably is between 15 and 60%. When the blackening temperature exceeds 600xc2x0 C., it is desirable that the final cold rolling reduction ratio be between 20 and 40%.
Stress relief annealing:xe2x80x94Although it has no effect upon creep elongation of the work after blackening, the annealing of this character is desirable since it controls uneven deformation due to release of the residual stresses during blackening. Stress relief annealing at 350 to 500xc2x0 C. for from 10 minutes to one hour after final cold rolling is recommended.